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Booklet No. 1 of 8:
PRODUCTION OF AMMONIA
EFMA European Fertilizer Manufacturers’ Association
Ave. E van Nieuwenhuyse 4 B-1160 Brussels Belgium
Best Available Techniques for Pollution Prevention and Control in the European Fertilizer Industry
Booklet No. 1 of 8:
PRODUCTION OF AMMONIA
Copyright 2000 – EFMA
This publication has been prepared by member companies of the European Fertilizer Manufacturers’ Association (EFMA). Neither the Association nor any individual member company can accept liability for accident or loss attributable to the use of the information given in this Booklet.
Booklet No. 1
Hydrocarbon feed Water Air
Urea Ammonia UAN
No. 2 No. 6
AN Nitric Acid
Phosphate rock K, Mg, S, micronutrients
NPK (nitrophosphate route)
Water Phosphate rock
K, Mg, S, micronutrients Phosphate rock
NPK (mixed acid route)
3 Cost of Pollution Control Measures 9.2 Storage Tanks 3. REFERENCES GLOSSARY OF TERMS APPENDIX 1 Emission Monitoring in Ammonia Plants APPENDIX 2 General Product Information on Ammonia 4 6 7 7 7 10 18 18 18 19 21 21 22 23 27 27 27 28 29 29 30 30 31 31 31 32 35 40 3 . OCCUPATIONAL HEALTH & SAFETY 8. EMISSION MONITORING 6. SUMMARY OF BAT EMISSION LEVELS 8.1 Achievable Emission Levels for New Plants 8.CONTENTS PREFACE DEFINITIONS 1. MAJOR HAZARDS 7. INTRODUCTION 2.2 Achievable Emission Levels for Existing Plants 8.4 Environmental Data for Ammonia Storage and Transfer 4.1 Introduction 3.2 BAT Production Processes 3.3 Transfer Equipment 4.1 Production Processes in Operation in Europe 2.2 Production Output 4. DESCRIPTION OF PRODUCTION PROCESSES 2. ENVIRONMENTAL DATA 4. DESCRIPTION OF STORAGE AND TRANSFER EQUIPMENT 3.1 Production Input Requirements 4.6 Emission Limits and Guideline Values for Ammonia Production in Some West-European Countries 5.3 Production Emissions and Wastes 4.5 Environmental Hazards Associated with Emissions and Wastes 4.
4 Phosphoric Acid No. 2 Nitric Acid No. The Booklets do not aim to create an exhaustive list of BAT but they highlight those most widely used and accepted. BAT covers both the technology used and the management practices necessary to operate a plant efﬁciently and safely. The Booklets give two sets of BAT emission levels:– For existing production units where pollution prevention is usually obtained by revamps or end-of-pipe solutions – For new plants where pollution prevention is integrated in the process design The emission levels refer to emissions during normal operations of typical sized plants. 5 Urea and Urea Ammonium Nitrate (UAN) No. 7 NPK Compound Fertilizers by the Nitrophosphate Route No. that good operational practices are vital for effective environmental management and that the principles of Responsible Care should be adhered to by all companies in the fertilizer business. 3 Sulphuric Acid (updated in collaboration with ESA) No. Other levels may be more appropriate for smaller or larger units and higher emissions may occur in start-up and shut-down operations and in emergencies. They have been prepared in order to share knowledge about BAT between the fertilizer manufacturers. The industry recognises. 6 Ammonium Nitrate (AN) and Calcium Ammonium Nitrate (CAN) No. They cover the production processes of the following products:No. The Booklets use the same deﬁnition of BAT as that given in the IPPC Directive 96/61 EC of 1996.PREFACE In 1995. however. 4 . as well as with the regulatory authorities. since good management is considered to be independent of the process route. 8 NPK Compound Fertilizers by the Mixed Acid Route The Booklets reﬂect industry perceptions of what techniques are generally considered to be feasible and present achievable emission levels associated with the manufacturing of the products listed above. 1 Ammonia No. These booklets were reviewed and updated in 1999 by EFMA experts drawn from member companies. The EFMA Booklets focus primarily on the technological processes. the European Fertilizer Manufacturers Association (EFMA) prepared eight Booklets on Best Available Techniques (BAT) in response to the proposed EU Directive on integrated pollution prevention and control (IPPC Directive).
eg from a total site area. EFMA would also advocate a further development for the authorisation of fertilizer plants. energy source and availability of raw materials If authorisation is given to exceed these BAT emission levels. depending on the method chosen and the precision of the analysis. It is important when issuing regulatory authorisations. this implies that emissions from single units should be allowed to exceed the values in the BAT Booklets. as discussed in these BAT Booklets. The plants can be complex. The emission levels are given both in concentration values (ppm. The given emission levels should not. therefore. EFMA recommends that the given emission levels should be used as reference levels for the establishment of regulatory authorisations. Finally. mg. with the integration of several production processes and they can be located close to other industries.m-3 or mg. Thus there should be a shift away from authorisation governed by concentration values of single point emission sources. be considered as absolute but as references which are independent of the methods used. to identify the monitoring method(s) to be applied. However. Deviations should be allowed as governed by:– Local environmental requirements. Existing plants should be given ample time to comply with BAT emission levels and care should be taken to reﬂect the technological differences between new and existing plants when issuing regulatory authorisations. April 2000 5 . Furthermore. A wide variety of methods exist for monitoring emissions. the Booklets do not cover noise. given that the global and inter-regional environments are not adversely affected – Practicalities and costs of achieving BAT – Production constraints given by product range.l-1) and in load values (emission per tonne of product). provided that the total load from the whole complex is comparable with that which can be deduced from the BAT Booklets. This approach will enable plant management to ﬁnd the most cost-effective environmental solutions and would be to the beneﬁt of our common environment. The Booklets provide examples of methods currently available. It should be noted that there is not necessarily a direct link between the concentration values and the load values. Differences in national practices may give rise to differing results as the methods are not internationally standardised. The emission levels given in the Booklets are subject to some variance. the reasons for the deviation should be documented locally.Only the more signiﬁcant types of emissions are covered and the emission levels given in the Booklets do not include fugitive emissions and emissions due to rainwater. Brussels. it should be emphasised that each individual member company of EFMA is responsible for deciding how to apply the guiding principles of the Booklets. It would be better to deﬁne maximum allowable load values from an entire operation. heat emissions and visual impacts.
maintained.DEFINITIONS The following deﬁnitions are taken from Council directive 96/61/EC of 1996 on Integrated Pollution Prevention and Control:“Best Available Techniques” mean the most effective and advanced stage in the development of activities and their methods of operation which indicate the practical suitability of particular techniques for providing. 6 . built. operated and decommissioned. “Best” means most effective in achieving a high general level of protection for the environment as a whole. where that is not practicable. in principle. whether or not the techniques are used or produced inside the Member State in question. generally to reduce emissions and the impact on the environment as a whole:“Techniques” include both the technology used and the way in which the installation is designed. “Available” techniques mean those developed on a scale which allows implementation in the relevant industrial sector under economically viable conditions. taking into consideration the costs and advantages. as long as they are reasonably accessible to the operator. the basis for emission limit values designed to prevent or.
000t. and energy. The total energy consumption for the production of ammonia in a modern steam reforming plant is 40-50% above the thermodynamic minimum. The energy source is usually hydrocarbons.800t.d-1 (500. Steam reforming of light hydrocarbons is the most efﬁcient route. a urea plant.2. The practical minimum consumption is assumed to be about 130% of the theoretical minimum. although capacities of 1. eg. air. and transfer. The description is partly based on Reference . 7 . but such integration is not covered in this Booklet. INTRODUCTION This Booklet covers Best Available Techniques (BAT) for ammonia production.d-1. but synthesis gas quality inﬂuences the loop design and operating conditions. DESCRIPTION OF PRODUCTION PROCESSES 2. A block diagram of the conventional steam reforming process is shown in Figure 1. with about 77% of world ammonia capacity being based on natural gas .500t. Further.y-1) will be considered as a standard capacity. thus providing hydrogen as well. but may also be coal or electricity. storage. either refrigerated at atmospheric pressure or non-refrigerated at ambient temperature. The typical size of a large single-train ammonia plant is 1. Coal gasiﬁcation and water electrolysis are no longer in use in the European ammonia industry. More than half of the excess consumption is due to compression losses. The equipment and machinery used in today’s large ammonia plants have achieved high reliabilities and technical on-stream factors in excess of 90% are common.000-1.1 Production Processes in Operation in Europe Two main types of production process for ammonia synthesis gas are currently in operation in Europe:– Steam reforming of natural gas or other light hydrocarbons (Natural Gas Liquids. the ammonia plant may stand alone or be integrated with other plants on the site. Ammonia is produced basically from water. untreated water and air. and ammonia product stored as liquid. Naphtha) – Partial oxidation of heavy fuel oil or vacuum residue In at least one partial oxidation unit. A process description is given in 2. In the case of steam and/or carbon dioxide export those battery limit conditions will depend on the receiver’s requirements. a separate auxiliary boiler is required). The process and energy systems are integrated to improve overall energy efﬁciency.1.1. The ammonia synthesis process is principally independent of the type of synthesis gas production process. Liqueﬁed Petroleum Gas. About 85% of world ammonia production is based on steam reforming concepts .d-1 and above are not uncommon for new plants. 2. In this Booklet 1. natural gas is used as feedstock.500t. (In some cases. Plant battery limits are generally feedstock and fuel supply by pipelines at sufﬁcient pressure for reforming.
Natural gas ZnO Desulphurisation ZnS H2O. Purge/flash gas NH3 Figure 1 – Block diagram of the steam/air reforming process. Power CO2 removal Condensate CO2 Methanation Power Compression Power Ammonia synthesis Heat. Power Primary reformer Flue-gas Secondary reformer Heat Shift conversion Heat Heat. 8 . Fuel Air.
Power Air O2 Heavy oil Gasification Heat Air Separation Unit Soot removal/recovery Slag Sulphur removal/recovery Sulphur H2 O Shift conversion Heat Heat. Power CO2 removal Condensate CO2 N2 Liquid N2 wash Fuel gas Power Compression Power Ammonia synthesis Heat. 9 . Flash gas NH3 Fuel Auxiliary boiler Flue-gas Figure 2 – Block diagram of the partial oxidation process.
The BAT reforming processes can be divided into the following types:– Conventional steam reforming with a ﬁred primary reformer and stoichiometric air secondary reforming (stoichiometric H/N-ratio) – Steam reforming with mild conditions in a ﬁred primary reformer and excess air secondary reforming (under-stoichiometric H/N-ratio) – Heat exchange autothermal reforming.4 Production cost 1.0 1. heavy oil and coal gasiﬁcation gives the following approximate relative consumption ﬁgures. A block diagram of a typical partial oxidation process is shown in Figure 2.0 1. Other BAT processes may also exist.5. All three reforming versions. The following description concentrates on presenting the conventional steam reforming process and only deviations and additions will be described for the other BAT processes. Natural gas reforming with steam and air is the simplest and most efﬁcient way of ammonia synthesis gas production. or in a combined autothermal reformer. and partial oxidation of heavy residues.7 Investment cost 1. using excess or enriched air (under-stoichiometric or stoichiometric H/N-ratio) For heavy feedstocks.0 1. and a process description is given in 2. based on world reserves and consumption rate. 10 . partial oxidation with oxygen is used in the synthesis gas production.2 BAT Production Processes No single process can be identiﬁed as BAT for the production of ammonia. 2. one might expect coal to take over. based on modern technological standards for each route.4 2.3 1. at European economic conditions:Natural Heavy Coal gas oil Energy consumption 1. with a process gas heated steam reformer (heat exchange reformer) and a separate secondary reformer. Comparing natural gas reforming.2. the steam/air reforming concepts based on natural gas and other light hydrocarbons are considered to be the dominating group of BAT production processes. 50-200 years.For heavier feedstocks than naphtha. partial oxidation is considered as the BAT production process.7 Based on the known resources of fossil raw materials. when natural gas is not available and the partial oxidation process could solve a waste problem (heavy residues. In this chapter the characteristics of BAT processes based on available feedstocks are described. plastics recycle). Heavy oil may be attractive under special environmental concerns. it is likely that natural gas will dominate as the feedstock for ammonia for the next 50 years at least. For the present time and the near future. are operated in Europe today.2 1. In the very long term.
1. part of the process steam is supplied by feed-gas saturation. In new plants the optimum S/C-ratio may be lower than 3. The feedstock normally contains up to 5mg S.1. The feed-gas is preheated to 350-400°C.3 Primary reforming The gas from the desulphuriser is mixed with process steam. The zinc sulphide remains in the adsorption bed. 11 .2. and then adsorbed on pelletised zinc oxide:R-SH + H2 H2S + ZnO H2S + RH ZnS + H2O In this way. and the plant steam balance.Nm-3 as sulphur compounds.1 Overall conversion The theoretical process conversions.2. purge gas recovery.24H2O N2 + 3H2 2NH3 0.1 Conventional steam reforming 2. The hydrogen for the reaction is usually recycled from the synthesis section. which should be around 3. are given in the following approximate formulae:0. shift operation. 2. For more detailed process ﬂow sheets refer to Ullmann .2.0. before entering the primary reformer. and then treated in a desulphurisation vessel.88CO2 + N2 + 3H2 The synthesis gas production and puriﬁcation normally take place at 25-35bar pressure. and the steam/gas mixture is then heated further to 500-600°C in the convection section before entering the primary reformer. usually coming from an extraction turbine.88CH4 + 1.2. (Special pre-reformer catalysts are offered by several suppliers).1ppm S in the gas feed.0 for the BAT reforming processes. based on methane feedstock. primary reformer capacity. The primary reformer consists of a large number of high–nickel chromium alloy tubes ﬁlled with nickel-containing reforming catalyst. The amount of process steam is given by the process steam to carbon molar ratio (S/Cratio). Also. In some new or revamped plants the preheated steam/gas mixture is passed through an adiabatic pre-reformer and reheated in the convection section.1. where the sulphur compounds are hydrogenated to H2S. typically using a cobalt molybdenum catalyst. in some plants.26Air + 1.2 Feedstock desulphurisation Most of the catalysts used in the process are sensitive to sulphur and sulphur compounds. The ammonia synthesis pressure is usually in the range 100-250bar. the sulphur is removed to less than 0. 2. The overall reaction is highly endothermic and additional heat is required to raise the temperature to 780-830°C at the reformer outlet.2. The optimum ratio depends on several factors. usually in the primary reformer convection section. such as feedstock quality.
000°C.5 Shift conversion The process gas from the secondary reformer contains 12-15% CO (dry gas base) and most of the CO is converted in the shift section according to the reaction:CO + H2O CO2 + H2 ∆H0298 = –41 kJ. This is done in the secondary reformer by internal combustion of part of the gas with the process air.mol-1 ∆H0298 = –41 kJ. where the CO content is reduced to about 12 .mol-1 The heat for the primary reforming process is supplied by burning natural gas or other gaseous fuel. the gas is passed through a bed of iron oxide/chromium oxide catalyst at around 400°C. The temperature must be raised to increase the conversion. The heat content (waste heat) of the ﬂue-gas is used in the reformer convection section. The reformer outlet temperature is around 1.2. and up to 99% of the hydrocarbon feed (to the primary reformer) is converted. The fuel energy requirement in the conventional reforming process is 40-50% of the process feedgas energy. giving a residual methane content of 0. In the conventional reforming process the degree of primary reforming is adjusted so that the air supplied to the secondary reformer meets both the heat balance and the stoichiometric synthesis gas requirement. in the burners of a radiant box containing the tubes. which also provides the nitrogen for the ﬁnal synthesis gas.1.2-0. The process gas is cooled to 350-400°C in a waste heat steam boiler or boiler/superheater downstream from the secondary reformer. The process gas is mixed with the air in a burner and then passed over a nickel-containing secondary reformer catalyst. The process air is compressed to the reforming pressure and heated further in the primary reformer convection section to around 600°C.2. after supplying the necessary high level heat to the reforming process. These emissions are mainly CO2. Thus only about 50-60% of the fuel’s heat value is directly used in the process itself. for various process and steam system duties.The composition of the gas leaving the primary reformer is given by close approach to the following chemical equilibria:CH4 + H2O CO + H2O CO + 3H2 CO2 + H2 ∆H0298 = 206 kJ.mol-1 In the High Temperature Shift (HTS) conversion. 2.4 Secondary reforming Only 30-40% of the hydrocarbon feed is reformed in the primary reformer because of the chemical equilibria at the actual operating conditions. The ﬂue-gas leaving the radiant box has temperatures in excess of 900°C. NOx.1.3% (dry gas base) in the process gas leaving the secondary reformer. The ﬂue-gas leaving the convection section at 100-200°C is one of the main sources of emissions from the plant. with small amounts of SO2 and CO. 2.
If all this lowlevel heat is used for CO2 removal or absorption refrigeration. The heat released during cooling/condensation is used for:– The regeneration of the CO2 scrubbing solution – Driving an absorption refrigeration unit – Boiler feedwater preheat The amount of heat released depends on the process steam to carbon ratio. The typical range of heat consumption in the modern chemical absorption process is 30-60MJ. CO2 and the excess process steam.2-0. high-level heat has to be used for the feedwater system. The gas from the HTS is cooled and passed through the Low Temperature Shift (LTS) converter. Residual CO2 contents are usually in the range 100-1. Activated Methyl DiEthanolamine (aMDEA) or hot potassium carbonate solutions. dependent on the type and design of the removal unit.2. or similar – Benﬁeld process (HiPure.4% (dry gas base). This LTS converter is ﬁlled with a copper oxide/zinc oxide-based catalyst and operates at about 200-220°C. N2.kmol-1 CO2. the mechanical energy requirements have also to be considered.1. An energy-efﬁcient process should therefore have a CO2 removal system with a low heat demand. The physical absorption processes may be designed for zero heat consumption. propylene carbonate and others. LoHeat). For new ammonia plants the following CO2 removal processes are currently regarded as BAT:– aMDEA standard 2-stage process.3% (dry gas base). There is a tendency to use copper containing catalyst for increased conversion. The residual CO content in the converted gas is about 0. limited by the shift equilibrium at the actual operating temperature. The MEA process has a high regeneration energy consumption and is not regarded as a BAT process. All these components should be stripped from the condensate and/or recycled in BAT processes. formic acid and acetic acid could be present in the condensate. The gas is cooled and most of the excess steam is condensed before it enters the CO2 removal system.000ppm of ammonia 800-1. A low residual CO content is important for the efﬁciency of the process. but for comparison with the chemical processes. or similar – Selexol or similar physical absorption processes Concepts such as Pressure Swing Adsorption (PSA) should also be regarded as BAT in some new plants but in such cases CO2 removal is not the only function of the PSA unit.200ppm of methanol. This condensate normally contains 1. Minor amounts of amines. 2. The solvents used in chemical absorption processes are mainly aqueous amine solutions (Mono Ethanolamine (MEA).000ppmv. The CO2 is removed in a chemical or a physical absorption process. 13 . Contents down to about 50ppmv are achievable. Physical solvents are glycol dimethylethers (Selexol).6 CO2 removal The process gas from the low temperature shift converter contains mainly H2.500-2.
2. thus maintaining the loop pressure. A make-up gas containing traces of water or carbon dioxide must be added before ammonia condensation. Conventional reforming with methanation as the ﬁnal puriﬁcation step.2. Methane is an inert gas in the synthesis reaction. A newly developed ammonia synthesis catalyst containing ruthenium on a graphite support has a much higher activity per unit of volume and has the potential to increase conversion and lower operating pressures. extensive heat exchange is required due to the exothermic reaction and the large temperature range in the loop. The synthesis of ammonia takes place on an iron catalyst at pressures usually in the range 100-250bar and temperatures in the range 350-550°C:N2 + 3H2 2NH3 ∆H0298 = –46 kJ. The loop purge should be taken out after ammonia separation and before make-up gas addition. The purge gas is scrubbed with water to remove ammonia before being used as fuel or before being sent for hydrogen recovery. Synthesis loop arrangements differ with respect to the points in the loop at which the make-up gas is delivered and the ammonia and purge gas are taken out.2. This is done ﬁrstly by cooling and condensation downstream of the methanator and ﬁnally by condensation/absorption in the product ammonia in the loop or in a make-up gas drying unit. and the reacted gas is substituted by the fresh make-up synthesis gas. needed for condensation of product ammonia. This conﬁguration is dependent on the make-up gas being treated in a drying step before entering the loop. with negative effects both to ammonia condensation and energy.1. The size of this purge stream controls the level of inerts in the loop to about 10-15%. The best arrangement is to add the make-up gas after ammonia condensation and ahead of the converter. 14 . The major part of these inerts is removed by taking out a purge stream from the loop. The refrigeration compressor.8 Synthesis gas compression and ammonia synthesis Modern ammonia plants use centrifugal compressors for synthesis gas compression. produces a synthesis gas containing inerts (methane and argon) in quantities that do not dissolve in the condensed ammonia. In addition. are poisonous for the ammonia synthesis catalyst and must be removed by conversion to CH4 in the methanator:CO + 3H2 CO2 + 4H2 CH4 + H2O CH4 + 2H2O The reactions take place at around 300°C in a reactor ﬁlled with a nickel containing catalyst. usually driven by steam turbines.2.mol-1 NH3 Only 20-30% is reacted per pass in the converter due to the unfavourable equilibrium conditions.7 Methanation The small amounts of CO and CO2. remaining in the synthesis gas. with the steam being produced in the ammonia plant.1. The ammonia that is formed is separated from the recycle gas by cooling/condensation. but the water must be removed before entering the converter. is also usually driven by a steam turbine.
2. the ﬁring efﬁciency increases.9 Steam and power system Steam reforming ammonia plants have high-level surplus heat available for steam production in the reforming. and the size and cost of the primary reformer are reduced.2.2 Steam reforming with excess air secondary reforming 2.1 Process ﬂowsheet Some processes are designed for reduced primary reforming by moving some of the duty to the secondary reformer because of the marginal low efﬁciency of the primary reformer. The process air requirement is about 50% higher than in the conventional process. to achieve sufﬁciently low ammonia concentrations in the gas recycled to the converter. and synthesis sections. Most of this waste heat is used for high pressure steam production for use in turbines for driving the main compressors and pumps and as process steam extracted from the turbine system. A brief description is given of features diverging from the conventional concept in the following paragraphs. The extent of reforming is reduced according to the lower heat supply and lower temperature. shift conversion. and in the convection section of the primary reformer.1.Ammonia condensation is far from complete if cooling is with water or air and is usually not satisfactory (dependent on loop pressure and cooling medium temperature).3 Increased process air supply to the secondary reformer Decreased heat supply in the primary reformer means that increased internal ﬁring is necessary to achieve approximately the same degree of total reforming. as methane is removed in the ﬁnal puriﬁcation step. The milder operating conditions prolong catalyst.2. 2.2 Decreased ﬁring in the primary reformer Decreased heat supply in the primary reformer means that the process outlet temperature is lowered (to about 700°C).2. catalyst tube and outlet header service lives. The process air compressor is usually driven by a gas turbine with the exhaust gas from the turbine being used as combustion air in the primary reformer. These features are:– Decreased ﬁring in the primary reformer – Increased process air ﬂow to the secondary reforming – Cryogenic ﬁnal puriﬁcation after methanation – Lower inert level of the make-up syngas 2. Some excess steam is available for export when using a gas turbine.2. and thus a lower secondary reformer outlet temperature is acceptable and preferable in this type of process. A modern steam reforming ammonia plant can be made energetically self-sufﬁcient if necessary. The ammonia vapours are liquiﬁed after recompression in the refrigeration compressor. This means increased compression capacity and energy. 15 . 2.2. compared to the conventional concept. A somewhat higher methane slip. Vapourising ammonia is used as a refrigerant in most ammonia plants. Generally. a slight decrease in steam to carbon ratio is acceptable. 2. but usually a small steam export and electricity import are preferred.2.2.
NOx emissions may be reduced by 50% or more.000°C. together result in a more efﬁcient process. by using the heat content of the secondary reformed gas in a newly-developed primary reformer (gas heated reformer.2. Recent developments are to recycle this heat to the process itself.2. 2. Developments are expected to go in the following directions:– Lowering the steam to carbon ratio – Shifting duty from primary to secondary reformer – Improved ﬁnal puriﬁcation – Improved synthesis loop efﬁciency – Improved power energy system – Low NOx burners – Non iron based ammonia synthesis catalyst The new autothermal concepts are expected to be developed further.d-1 can be built. except for a small amount of argon. Recently it has been reported that capacities in the range of 1. Surplus air or oxygen-enriched air is required in the secondary reformer to meet the heat balance in this autothermal concept. Two processes of this kind are in operation. compared to the conventional puriﬁcation by methanation only.800t. both at temperatures around 1.2.4 Cryogenic ﬁnal puriﬁcation In the cryogenic puriﬁer all the methane and the excess nitrogen are removed from the synthesis gas as well as a part of the argon. 2. 2. The cryogenic unit also receives the purge from the synthesis section and delivers an off-gas for fuel.2.5 Lower syngas inert level The removal of essentially all impurities from the make-up synthesis gas is a signiﬁcant improvement. Higher conversion per pass and reduced purge ﬂow. heat exchange reformer).2. and will continue the developments outlined above. Emissions to the atmosphere are reduced signiﬁcantly by eliminating the ﬂue-gas from the primary reformer. The puriﬁed syngas is then practically free of all impurities.3 Heat exchange autothermal reforming From a thermodynamic point of view it is wasteful to use the high-level heat of the secondary reformer outlet gas and the primary reformer ﬂue-gas.2. The cooling is produced by depressurisation and no external supply is needed.2. compared to conventional steam reforming. simply to raise steam. thus eliminating the ﬁred furnace. and some others are at the pilot stage. All these processes are considered as BAT production processes. 16 . depending on the extent of auxiliary combustion in the plant.4 BAT reforming processes for new plants The modern versions of the conventional steam reforming and excess air reforming processes will still be used for new plants for many years to come.
The process gas is freed from solids by water scrubbing after waste heat recovery and the soot is recycled to the feed. The ﬂue-gas from these power plants is the main source of emissions which are mainly SO2. The nitrogen is added in the liquid nitrogen wash to remove impurities from the synthesis gas and to get the required hydrogen/nitrogen ratio in the synthesis gas.5O2 CO + n/2H2 Carbon dioxide. The heavy metals. The ammonia synthesis is quite similar to that used in steam reforming plants. In at least two units in Europe. The site emissions are very low if the compressors are driven by imported electric power. The partial oxidation process offers an alternative for future utilisation of such wastes.5. Some steam is added for temperature moderation. such as V. The sulphur compounds in the feed are converted to hydrogen sulphide.2.2. The simpliﬁed reaction pattern is:–CHn – + 0. The hydrogen sulphide in the process gas is separated in a selective absorption step and reprocessed to elementary sulphur in a Claus unit. methane and some soot are formed in addition. In this unit practically all the impurities are removed and nitrogen is added to give the stoichiometric hydrogen to nitrogen ratio. before ﬁnal puriﬁcation by a liquid nitrogen wash.400°C. but simpler and more efﬁcient.5.2 Steam and power system Auxiliary boilers are required if the compressors are steam-driven. to avoid ash build-up in the gasiﬁcation cycle downstream units. Mineral compounds in the feed are transformed into speciﬁc ashes. 17 . CO2 is removed by using an absorption agent which might be the same as that in the sulphur removal step. the soot is separated from soot water in a mainstream ﬁltration stage. due to the high purity of synthesis gas from liquid nitrogen wash units and the synthesis loop not requiring a purge. The shift conversion usually has two high temperature shift catalyst beds with intermediate cooling.1 Process description The partial oxidation process is used for the gasiﬁcation of heavy feedstocks such as residual oils and coal. The partial oxidation gasiﬁcation is a non-catalytic process taking place at high pressure (>50bar) and temperatures around 1. Ni and Fe are recovered. Residual traces of absorption agent and CO2 are then removed from the process gas.5 Partial oxidation of heavy oils 2.2.2. Steam for the shift conversion is supplied partially by a cooler-saturator system and partially by steam injection. 2. The ash compounds are drained with the process condensate and/or together with a part of the soot. Extremely viscous hydrocarbons and plastic wastes may also be used as fractions of the feed. and CO2. An air separation unit is required for the production of oxygen for the partial oxidation step. NOx.
DESCRIPTION OF STORAGE AND TRANSFER EQUIPMENT 3.5. 3. schools. since these could increase the possibility of a release of ammonia. 3.2. It is undesirable for ammonia storage tanks to be sited close to installations where there is a risk of ﬁre or explosion. Where there are no formal controls.3 Future improvements No major improvements are to be expected concerning process efﬁciency and plant investment costs. constructed. the effects of a major leak on areas of high population density could be very serious. partial oxidation will continue to be interesting in the future. In some countries there are planning procedures or regulations which control the siting of ammonia storage installations and similar establishments. even though the residual risk is small. Major leaks of ammonia from storage tanks are almost unknown with most of the leaks which do occur being during transport or transfer.000 to 30.700 tonnes – Semi-refrigerated tanks Emissions during normal operation are negligible. However. the siting of ammonia storage facilities should be given serious consideration at the design stage. due to its feedstock ﬂexibility. rail tank cars or ships. It is therefore good practice to build ammonia storage and handling installations at a sufﬁcient distance from domestic housing. However. Ammonia is usually stored by using one or other of three methods:– Fully refrigerated storage in large tanks with a typical capacity of 10. hospitals or any area where substantial numbers of people may assemble. The separation and disposal of the soot and especially the ashes are necessary to adapt to deteriorating residue qualities or alternative raw material sources.2 Storage Tanks Anhydrous ammonia is stored in three types of tank as outlined above:– Fully refrigerated at a temperature of about –33°C.1 Introduction Liqueﬁed ammonia from production plants is either used directly in downstream plants or transferred to storage tanks. A well designed. these tanks are provided with refrigeration equipment – Non-refrigerated tanks in which the ammonia is stored at ambient temperature – Semi-refrigerated spheres 18 .2.000) – Pressurised storage spheres or cylinders up to about 1. From these the ammonia can be transferred to road tankers.000 tonnes (up to 50. operated and maintained installation has a very low probability of an ammonia leak of hazardous proportions.
therefore. There should be at least two refrigeration units to allow proper maintenance and to prevent the emission of ammonia via the relief valves. each having a high level alarm. The roof rests on the inner wall – Full containment: the two walls of this closed storage tank are also designed to contain the stored amount of liquid. The ﬂare must be located at a suitable distance from the tanks. The main isolation valves should be backed up by remotely operated valves. The storage tank must be safeguarded against high pressure and in the case of refrigerated liquid ammonia also against a pressure below the minimum design pressure.3 Transfer Equipment Liquid or gas pipelines should be ﬁtted with isolation valves. Furthermore. or recognised international. There are several construction types for the storage of refrigerated liquid products. Liquid ammonia has a high thermal coefﬁcient of expansion and. normally with a containment bund around it – Double containment: this type of storage tank has two vertical walls. should be installed on the feeding line. an installed alternative power supply may be necessary. The ingress of warm ammonia into cold ammonia must be avoided to eliminate risk of excessive evaporation and the “roll-over” phenomenon. 3. The design and materials of construction of the tank should be checked by consulting an appropriate national. both of which are designed to contain the stored amount of liquid and withstand the hydrostatic pressure of the liquid. standard. some means of safe venting should be provided on pipelines in which any signiﬁcant quantity can be trapped between valves. In cases of refrigerated liquid ammonia. The initial release of ammonia in the case of a line or tank failure is much slower than with pressurised ammonia. but in this case the roof rests on the outer wall The tank must be constructed in conformity with an agreed code for the construction of pressure vessels or storage tanks and taking account of its pressure and operating temperature. operated by a very high level alarm instrument.Refrigerated storage is preferred for storage of large quantities of liquid ammonia. The remote systems should be of such a type that closure is automatic in case of a power failure. appropriate for the duty using an adequate margin between operating and relief pressure. storage tanks must be equipped with a recompression installation to liquefy the boil-off. 19 . An automatic discharge system to a ﬂare may be provided in case of failure of the refrigeration equipment. These could make demands on the blast resistance of storage tanks in some cases. Relief valves should be provided. The most important types are:– Single containment: a single-wall insulated tank. All storage tanks should be equipped with two independent level indicators. etc. An automatic cut-off valve.
3. an ammonia vapour network of the site or to a scrubber/absorber. Preferably. this should be done by using a pressurised inert gas such as nitrogen or ammonia vapour. The ammonia vapours can be transferred during (un)loading to a storage tank. Ammonia is transported in road tankers. The isolation valves must be closed automatically. After each loading-unloading operation. Both liquid and vapour return lines should be present for import and export terminals. There should be a scrubbing system or a ﬂare in the event of venting inert gas.Liquid ammonia pipelines should be ﬁtted with remotely operated valves at suitable intervals to minimise the loss in the event of a line failure. A vapour return line is not necessary when the ship has sufﬁcient refrigeration capacity or for the import of ammonia only. Loading arms are then purged by inert gas or ammonia vapour. Both liquid and vapour connections must be equipped with isolation valves as near to the ship as possible. The ends of loading and unloading arms should be equipped with dry break couplings. Modern road and rail car loading stations are equipped with a safeguard against overﬁlling. to prevent emissions to the atmosphere. During (un)loading a minimum safety distance to other ships must always be maintained around the ship (eg. when these couplings are disconnected or when the (un)loading arms are too far out of position. attention should be paid to avoid getting the inert gas into tankers and storage tanks.3. A weigh check must be carried out after the loading. 30m). Before disconnection of equipment after (un)loading the liquid ammonia in these parts must be removed to one of the reservoirs.2 Ships Loading and unloading of ships is only permitted at sites which are authorised for this purpose. There should be a scrubbing system or ﬂare in case the inert gas has to be vented.1 Railroad and road loading Loading and unloading of rail tank cars and road tankers is usually done by loading arms. 3. If inert gas is used. During (un)loading both the liquid supply and vapour return lines must be connected to the transport medium. 20 . It must be possible to close these valves quickly under all conditions and the connection between tank and liquid line must be equipped with an isolation valve. to ensure that the maximum allowable content has not been exceeded. attention should be paid to avoid getting inert gas into tankers and storage tanks. liquid ammonia contained within loading arms must be collected in a suitable evaporation tank connected to the storage tank through the vapour line.3. If inert gas is used. rail tank cars (both pressurised) and ships (pressurised or refrigerated).
1. usually from an extraction turbine.5kg.2 Fuel Assuming an efﬁcient stand-alone plant with no energy export and no other import than feedstock and fuel.1.t-1 NH3 The uncertainty in autothermal reforming is mainly due to the type of compressor drives. This will be 0.4. 4.4-7.t-1 NH3 Autothermal reforming : 24.7-1. data for production will be given the highest attention.8 GJ(LHV). Boiler feedwater: Assuming all steam condensates are recycled.1kg air.85kg N2.2 GJ(LHV). respectively. Air and/or water for cooling: Will differ from one site to another. the fuel requirements are (approximately):Conventional reforming: 7.kg-1 NH3 in total). but additional steam is needed in shift conversion (1. ENVIRONMENTAL DATA Environmental data for the BAT production processes are generally known with a high degree of reliability.0 GJ(LHV).8 GJ(LHV). In the partial oxidation process the amount of air fed to the air separation unit is approximately 4kg.2kg. Hence.t-1 NH3 Autothermal reforming : 3.t-1 NH3 * Lower Heating Value 4. The net consumption according to the stoichiometic conversion is 0.kg-1 NH3.4 GJ(LHV).kg-1 NH3 (see above).t-1 NH3 Partial oxidation : 28.0 GJ(LHV).2 GJ(LHV). ie.6-0. depending on process condensate recycle or not.t-1 NH3 Excess air reforming : 23.t-1 NH3 Partial oxidation : 5.1 GJ(LHV*). Process air supply: In conventional reforming the nitrogen supply equals the ammonia nitrogen content plus the purge losses. In the excess air reforming and gas heated reformer cases the process air requirements are about 50% and 100% higher.kg-1 NH3. Small additional losses and potential import/export have to be allowed for in practice.1.kg-1 NH3.7kg.kg-1 NH3.1 Feedstock The typical feedstock requirements for modern plants are (approximately):Conventional reforming: 22. about 0.2-9.kg-1 NH3 or about 1.1 Production Input Requirements 4. only the process steam consumption has to be replaced by outside water. the total supply at a S/C ratio of 3.4-9. 21 . In partial oxidation much less steam is fed to the gasiﬁcation reactor. 4.0 will be about 1.5kg.3 Water and air In the steam reforming processes process steam is taken from the plant steam system. while data for storage and transfer are more uncertain and of much less importance. based on the oxygen requirement.6-7.t-1 NH3 Excess air reforming : 5.
based on average ﬁlling volumes and normally recommended operating periods. 4. The usual treatment additives and regeneration agents are used in the boiler feedwater preparation units. This includes imported power and/or auxiliary steam for driving the machinery. are given in the table below. In such cases the total energy consumption may be lowered and approach the present practical minimum of 27 GJ(LHV).1. 22 . 4. Solvent losses are mainly caused by leaks.8-31.04kg.d-1.1-37.4 Solvents and additives The consumption of solvent in the CO 2 removal unit should not normally exceed 0.000-500.h-1 for a BAT capacity plant.4.y-1 1 5 5 4 10 20 2 10 Actual consumptions in existing plants may differ considerably from the guidance ﬁgures above. In partial oxidation plants the total energy requirement is 36.t-1 NH3 for a stand-alone plant with no energy export and no other import than feedstock and fuel.500t.02-0. A part of the power needed may then be imported from a more efficient power plant outside the process plant.000t.2 Production Output 4. When using process waste heat in a gas heated reformer.t-1 NH3.1.000-1.t-1 NH3.2.t-1 NH3.y-1).5GJ (LHV). or about 2kg. The consumption ﬁgures should not differ from those of a standard steam boiler plant at the same location.8)GJ(LHV). for a gas based conventional reforming plant.1 Ammonia Ammonia production in the typical size BAT plant is 1. 4.1. the process itself will not produce enough steam to drive all the compressors.d-1 (300.5 Catalysts Approximate consumption ﬁgures.6 Energy requirements The total energy requirement in the reforming BAT processes is 28. m3. Catalyst type Hydrodesulphurisation Sulphur removal Primary Secondary reforming High temperature shift Low temperature shift Methanation Synthesis Typical replacement. The consumptions refer to a capacity of 1.500t.9(35. The production not used in downstream plants on site is stored as described in Chapter 3.
Processes with gas heated primary reforming may be designed for zero steam export even with some power import or gas turbine drive. The partial oxidation process has a steam deﬁcit if all compressors are steam driven. 99. Steam export is usual in excess air reforming processes where the process air compressor is driven by a gas turbine. Carbon dioxide in the combustion gases is not included in the above ﬁgures. and in cases when electric power is used for driving one or more of the main compressors.4 Steam export Modern steam reforming processes can be designed with no steam export or with some export of low/medium pressure steam if this can be favourably used on site.2. 4. 99. dependent on feedstock C/H ratio. The carbon dioxide production in steam/air reforming of natural gas is 1. but is shown in Figure 3.2 Carbon dioxide Carbon dioxide is produced according to the stoichiometric conversion and may be recovered for down-stream uses.15-1. the stoichiometric ratio for urea production.30kg.2. 4.2% wt) – Anhydrous ammonia min.29). is obtainable in the heat exchange reformer concepts.2.5 (weight ratio 1.7 wt %. stufﬁng boxes etc.3 Production Emissions and Wastes 4.6kg.3 Sulphur In BAT partial oxidation most (87-95%) of the sulphur content of the feed to the gasiﬁer is recovered in the Claus unit. A CO2/NH3 mole ratio of 0.kg-1 NH3. dependent on the degree of air reforming.Commercial anhydrous ammonia has two grades of purity:– Anhydrous ammonia min. In partial oxidation of residual oils the CO2 production is 2-2.3.1 Emissions into air from steam reforming plants From steam reforming plants with a ﬁred primary reformer emissions into air come from the following sources:– Flue-gas from the primary reformer – Vent gas from CO2 removal – Breathing gas from oil buffers (seals/compressors) – Fugitive emissions (from ﬂanges.9 wt % 4. water content (about 0.) – Purge and ﬂash gases from the synthesis section (usually added to the primary reformer fuel) – Non-continuous emissions (venting and ﬂaring) 23 .kg-1 NH3. 4.
24 .03 " Fuel Primary reformer Air Secondary reformer Shift conversion Condensate recycled CO2: 1200 kg.t-1 NO2: 1 " SO2: <0.01 " CO : <0.Natural gas Desulphurisation Flue-gas: CO2: 500 kg.t-1 CO2 removal Methanation Compression Ammonia synthesis NH3 -free purge gas to fuel NH3 Figure 3 – Typical emission levels in gas-based steam reforming plants with a gas-ﬁred primary reformer and process condensate recycle.
4. In some cases. (<0.t-1 NH3. (<0.1. before routing the off-gases to the primary reformer fuel gas system.3. Some plants without a ﬂare.4 Fugitive emissions The diffuse emissions from ﬂanges.Nm-3. The off-gases are thus combusted and end up as part of the ﬂue-gas. high purity CO2 is used. for a gas-based conventional steam reforming plant producing 1.1. The ﬂue-gas volume from excess air reforming may be lower.000Nm3. It is important to remove the ammonia as far as possible. at 3% (dry gas base) oxygen.Nm-3.d-1.3.500t. 25 . The other pollutants in the ﬂue-gas are:NOx: 200-400mg. should be minimised. 4. The CO2 contains small traces of synthesis gas and absorption solvent vapour. (98-195ppmv).3kg. while an airCO2 mixture from a stripping column is vented.6 Non-continuous emissions Emission of NOx during ﬂaring synthesis gas at start-up or trip situations is estimated to be 10-20kg. depending on the CO2 requirements of other production facilities on the site.01kg.1. is approximately 200. 4.1. stufﬁng boxes etc. and the purge gas may be treated in a recovery unit.3.3.3. vent to the atmosphere.1 Flue-gas from the primary reformer The ﬂue-gas volume. 4.h-1.t-1 NH3 expressed as NO2 SO2: 0.3. or 0.6-1. corresponding to 500kg CO2.2 Vent gases from CO2 removal More or less of the CO2 product may have to be vented.5 Purge and ﬂash gases The purge and flash gases from the synthesis section are usually washed with water to remove/recover ammonia.1.4.1.t-1) The NOx emission depends on several factors and the following features reduce the emission:– Low combustion air and fuel gas preheat – Steam/inert injection – Low ammonia content in injected purge-gas – Low excess oxygen – Low NOx burners – Post-combustion measures The SO2 emission comes from the sulphur in the fuel gas and can be calculated by a simple mass balance. as it will contribute considerably to the ﬂue-gas NOx emission. synthesis gas and lube oil. depending on fuel CO: <10mg. containing about 8% CO2 (dry gas base).t-1).Nm-3.1-2mg.h-1 as NO2 .03kg. 4.3 Breathing gas from oil buffers This contains traces of NH3 .
as these processes have much more internal combustion than the ﬁred reformer processes because all the reforming process heat is generated by internal combustion. Total recycle is obtained in this way. Reduction of NOx emissions by 80% has been claimed. may occur due to process condensates or due to the scrubbing of waste gases containing ammonia. during normal operation. In some cases the process condensate is used for feed-gas saturation and thus recycled to the process. 100ppmv).3.4 Emissions into water Pollution problems related to water. 50mg. This means that the CO2 emission from partial oxidation plants (max 1. NOx emission (max.3ppmv). soot and ash removal may cause pollution problems. In partial oxida- 26 . Spent catalysts and mol.Nm-3) is higher than in the reformer ﬂue-gas.3 Emissions into air from partial oxidation plants The partial oxidation process has the same emission sources as described for the reforming process except for the primary reformer ﬂue-gas. 4. Total CO2 emissions are ﬁxed by the energy consumption. Tail gas from sulphur recovery will also contain sulphur oxides. A partial oxidation plant may also have auxiliary boiler(s) for power steam production. Traces of soot and slag are emitted to water. and dust (traces. 4. Excess nitrogen is usually vented. max. In partial oxidation.500mg. if not properly handled. For self-sufﬁcient plants the ﬂue-gas volume in heat exchange reforming is about 50% of the ﬁgure for conventional steam reforming. 700mg. of the order of 1m3 per ton NH3 produced.3. Other additional emissions may be H2S (0. Usually the ammonia absorbed from purge and ﬂash gases is recovered in a closed loop so that no aqueous ammonia emissions occur. Emissions into water from the production plant during normal operation can thus be fully avoided. methanol (max. Process condensate is found primarily in the condensation section prior to the CO2 removal. CO (30ppmv). 4. The stripped condensate can be re-used as boiler feedwater make-up after treatment by ion exchange. Without treatment this condensate can contain up to 1kg of ammonia and 1kg methanol per m3.4. More than 95% of the dissolved gases can be recovered by stripping with process steam and are recycled to the process.sieves have to be removed and valuable metals are recovered from them.Nm-3) depends on the factors listed for the reformer ﬂue-gas and the nitrogen content of the fuel. The fuel to the auxiliary boiler/superheater together with possible scrubbing equipment determines the amount of CO2 in the ﬂue-gas. Soot from gasiﬁcation in partial oxidation processes is usually recovered and recycled to the process. In plants with power import the ﬂue-gas volumes are lower.3.5 Solid wastes The BAT ammonia processes do not normally produce solid wastes.Nm-3).2 Emissions into air from heat exchange reforming The ﬂue-gas volume (from auxiliary ﬁred equipment) and thus NOx and CO2 emissions are considerably reduced.3. if more efﬁciently off-site produced power is not available.
Very often the values are the subject of negotiations between the operator and the authority responsible for granting licences. the cold losses are balanced by recompressing and recondensing the evaporated ammonia. In practice. these authorities are of local character. 27 . During recompression.6 Emission Limits and Guideline Values for Ammonia Production in Some West-European Countries Two types of emission values are of importance:– Legally binding emission limit values for speciﬁc pollutants which apply for ammonia production – Guideline values which are not legally binding but provide the background for requirements laid down in individual permits Speciﬁc legally binding emission limits for ammonia production are only laid down in Germany. only the NOx and CO2 emissions have to be considered. the licensing authorities take into account emission limits applied in other countries. Small continuous emissions may thus occur. Generally the emissions from modern ammonia plants have little environmental impact. different air pollution requirements may apply for comparable plants. The ash can be upgraded and used as an ore substitute. no national emission limits or guidelines are ﬁxed for ammonia production plants. 4. in their negotiations with operators. At least in the Benelux countries and Ireland. More detailed information is given in Reference .5 Environmental Hazards Associated with Emissions and Wastes The production of ammonia is relatively clean compared to many other chemical processes. in particular those laid down in Dutch and German law. some inerts containing also traces of ammonia cannot be condensed but must be ﬂared or scrubbed with water. 4. With regard to the other countries. In some countries. During the normal operation of a reforming plant. Indirectly. Speciﬁc emission guideline values are laid down in the United Kingdom. The emissions from a ﬁred reformer or auxiliary boilers should conform with emission limits and guideline values adopted by the Council of EC in Directive 88/609/EEC or applied by the state. these values play the role of guideline values. the emission limits laid down for combustion installations play an important role because the energy consumption of an ammonia plant is relatively high. in addition to minor non-continuous emissions during loading operations. In the Netherlands and in Germany limits for emissions from boilers have been laid down which include chemical reactors.4 Environmental Data for Ammonia Storage and Transfer In a refrigerated storage. 4.tion plants sulphur is recovered in the Claus plant and can be used as feedstock in sulphuric acid units. so that even within one and the same country. In partial oxidation plants with oil-ﬁred auxiliary boilers the reduction of SO2 emissions can be achieved by using low sulphur fuel oil.
Methods for discontinuous and continuous measurements of NOx. Non-continuous and fugitive emissions are difﬁcult to measure.5. Traces of H2S are measured by lead acetate. In existing plants without recycle of process condensate. and CO in the ﬂue-gas from steam reforming processes with a ﬁred primary reformer and/or auxiliary boilers – SO2 from the sulphur removal and recovery systems in partial oxidation processes – CO2 and traces of removal solvents and synthesis gas in vent streams from the CO2 removal system – Small non-continuous and fugitive emissions – NH3 and methanol in process condensates (if not recycled) The following emissions into air should be monitored as part of a proper supervision:– NOx in ﬂue-gases – SO2 in ﬂue-gases (may be calculated by mass balance instead of monitoring emission. Verein Deutscher Ingenieure. Chemiluminescence or photometry are the most widely used methods for NOx. SO2 is determined by Infra Red (IR) absorption techniques. the emissions of pollutants to be expected from ammonia production are mainly:– CO2. AFNOR. SO2 and H2S are available and are to a large extent standardised at national level (Norme Belge/Belgische norm. EMISSION MONITORING As outlined in Chapter 4. CO emission is ﬁxed by the operating conditions and usually stable and low. the ammonia and methanol content should be monitored. A description of available methods for monitoring emissions is given in Appendix 1. Emissions into water from new plants are virtually zero as process condensates are recycled and monitoring is not normally required. Under normal operating conditions. NOx. British Standard. The frequency of monitoring depends on local circumstances and the operating stability of the actual plant. Nederlands Normalisatie Instituut). SO2. CO2 emission can be calculated from fuel speciﬁcation and energy consumption. 28 . if S input is known) – SO2 and H2S from sulphur removal/recovery systems in partial oxidation processes The other emissions into air need not be monitored. measurements once a month are usually sufﬁcient.
In ammonia plants CO2 and N2 are potentially suffocating gases. Appropriate precautions to protect both the operators and the local population are taken in the design and operation of the plants. In partial oxidation plants H2S and SO2 are present in the sulphur removal/recovery sections. Conﬁned explosions in ammonia plants appear to be limited to explosions equivalent to a few hundred kg TNT. from a storage tank) may be much more serious for the local population. In addition there is also the potential for toxic hazard due to the handling and storage of liquid ammonia. hydrogen). 7. The most important toxic components are CO from potential leaks in the synthesis gas generation and shift areas and NH3 from leaks in the ammonia synthesis and ammonia handling areas. especially when these occur in the feed-gas and synthesis gas systems (hydrocarbons. The following credible major hazards events are identiﬁed in an ammonia production plant:– Fire/explosion hazard due to leaks from the hydrocarbon feed system – Fire/explosion hazard due to leaks of synthesis gas in the CO removal/synthesis gas compression areas (75% hydrogen) – Toxic hazard from the release of liquid ammonia from the synthesis loop In ammonia storage the release of liquid ammonia (by sabotage) is a credible major hazard event. Traces of carbonyls (iron and nickel) may form during operation. covering the operators and the local population must be maintained. Suffocation due to lack of oxygen may occur at points where the breathing air has been diluted with inert gases. An emergency plan for this event. Fires and explosions are usually not a hazard or only a minor hazard to the local population although potentially most severe for the plant operators. The same is true for ﬁre balls equivalent to 500kg hydrogen. OCCUPATIONAL HEALTH & SAFETY The occupational health and safety issues associated with ammonia production and storage are:– Fire/explosion injuries – Poisoning – Suffocation Fires or explosions from the involuntary ignition of leaks are credible. The toxic hazard of a potential large release of liquid ammonia (ie. 29 . and thus in most cases not severe for people outside the plant fence. MAJOR HAZARDS Historical data show that the major accidents in ammonia plants are explosions and ﬁres. Such explosions are normally not fatal for humans at 50-60m distance.6.
not accounting for peaks which can occur during the unsteady transient conditions of start-up and shut-down and during emergencies.1. 8. <0. 8.000 30.ACGIH  occupational exposure limits for ammonia and other components associated with ammonia production are given in the table below.t-1 of product 8. In new reforming plants the total energy consumption should not exceed 29. All the ﬁgures are ppmv:Component TLV-TWA (8hr) TLV-STEL (15min) 25 35 NH3 NO2 3 5 SO2 2 5 10 15 H2S CO 50 400 CO2 5.3 Waste material Spent catalysts etc.Nm-3 kg.t-1 of product 75 150 0. Ammonia plants have high technological standards and need professional management.1 Achievable Emission Levels for New Plants The following emission levels can be achieved for new ammonia plants.3GJ(LHV). SUMMARY OF BAT EMISSION LEVELS 8. 8.t-1 of product Reclaiming of raw materials from spent catalyst by specialised companies prior to their disposal is common practice in the ammonia industry.t-1 and process condensate recycle should be a pre-requisite.45 NOx (as NO2 at 3% O2) SO2 (partial oxidation plants): as for combustion plants.2kg.1 Emissions into air ppmv mg. Precautions taken to prevent accidents and injuries during operation are incorporated in the operating and safety procedures for the plant.1. General product information on ammonia is given in Appendix 2.000 The ﬁgures are subject to updating and may vary between European countries.1kg. operating and maintenance working routines and personnel.2 Emissions into water NH3 or NH4 (as N) 0.1. Full health and safety information is given in Safety Data Sheets which must be available and updated. These levels relate to steady-state production. 30 .
8. these levels do not account for peak values during unsteady or transient conditions.9 to 3. ISBN 1-873387-26-1.  Appl.2 Achievable Emission Levels for Existing Plants The following emission levels can be achieved for existing ammonia plants. OH: ACGIH. Process condensate recycle can be included to bring existing plants to BAT standards for emissions into water and a rough investment of the order of 2. when authorised locally.2. 1997. REFERENCES  Commission of the European Communities Integrated Pollution Prevention and Control “Best Available Technique Reference Document on Ammonia Production.500t.9 NOx (as NO2 at 3% O2) SO2 (partial oxidation plants): as for combustion plants.t-1 of product 150 200-400 0.t-1 of product 8. M: Ammonia.  Appl.1 Emissions into air ppmv mg. As for new plants. 8. – ISBN 1-882417-03-8.8. Methanol.d-1). 1993-1994. 31 .2.t-1 of product 8. it is more economic to incorporate the pollution abatement system at the process design stage rather than revamping or “adding-on” equipment at a later stage.3 Cost of Pollution Control Measures The costs of pollution control measures in the fertilizer industry are difﬁcult to generalise as they depend on a number of factors such as:– The emission target or standard to be met – The type of process. production volumes. March 1997. Germany. M: Ammonia.2.2 Emissions into water NH3 or NH4 (as N) 0. – Whether the plant is new so that the design can be optimised with respect to pollution abatement. American Conference of Governmental Industrial Hygienists (ACGIH). Cincinnati. Published by Wiley-VCH. Principles and Industrial Practice. Modern Production Technologies. or whether the plant is an existing one requiring revamping or end-of-pipe pollution abatement equipment Generally. Hydrogen.  Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices. Contributions from ammonia-containing purge gases can be excluded from these ﬁgures in special cases.3 Waste material Spent catalysts etc. 9.3million EUR can be anticipated (1. 1998 ISBN 3-527-29593-3. Carbonmonoxide. Weinheim.Nm-3 kg.2kg.1kg. type of raw materials being used etc. the degree of integration with other processes on site. British Sulphur Publishing. <0.
GLOSSARY The following abbreviations occur frequently throughout the series of Booklets but without necessarily appearing in each Booklet:ACGIH AFNOR AN AQS AS BAT BATNEEC BOD BPL BS CAN CEFIC COD DAP DIN EEC EFMA ELV ESA EU IFA IMDG IPC IPPC ISO MAP MOP NK NP NPK NS OEL SSP STEL TLV TSP TWA UAN 32 American Conference of Governmental Industrial Hygienists Association Française de Normalisation (France) Ammonium Nitrate Air Quality Standard Ammonium Sulphate Best Available Techniques Best Available Technology Not Entailing Excessive Cost Biological Oxygen Demand Basic Phosphate of Lime (Bone Phosphate of Lime) British Standard Calcium Ammonium Nitrate Conseil Europeen de l’Industrie Chimique (European Chemical Industry Council) Chemical Oxygen Demand Di-Ammonium Phosphate Deutsches Institut für Normung (Germany) European Economic Community European Fertilizer Manufacturers Association Emission Limit Value European Sulphuric Acid Association European Union (Formerly. European Community. Phosphate and Potash Fertilizer containing Nitrogen and Sulphur Occupational Exposure Limit Single Super-Phosphate Short Term Exposure Limit Threshold Limit Value Triple Super-Phosphate Time Weighted Average Urea Ammonium Nitrate (Solution) . EC) International Fertilizer Industry Association International Maritime Dangerous Goods (Code) Integrated Pollution Control Integrated Pollution Prevention and Control International Standards Organisation (International Organisation for Standardisation) Mono-Ammonium Phosphate Muriate of Potash (Potassium Chloride) Compound fertilizer containing Nitrogen and Potash Compound fertilizer containing Nitrogen and Phosphate Compound fertilizer containing Nitrogen.
C CaCO3 Cd CH3OH CH4 CO CO2 F F– H (H2) H2O H2S H2SiF6 H2SO4 H3PO4 HNO3 K KCl K2O N (N2) N2O NH3 NH4-N NH4NO3 NO NO2 NO3-N NOx O (O2) P P2O5 S SO2 SO3 Carbon Calcium Carbonate Cadmium Methanol Methane Carbon Monoxide Carbon Dioxide Fluorine Fluoride Hydrogen Water Hydrogen Sulphide Hydroﬂuorosilicic Acid (Hexaﬂuorosilicic Acid) Sulphuric Acid Phosphoric Acid Nitric Acid Potassium Potassium Chloride (Muriate of Potash) (“Potash”) Potassium Oxide Nitrogen Dinitrogen Monoxide (Nitrous Oxide) Ammonia Ammoniacal Nitrogen Ammonium Nitrate Nitrogen Monoxide (Nitric Oxide or Nitrogen Oxide) Nitrogen Dioxide Nitric Nitrogen Oxides of Nitrogen (Excluding Nitrous Oxide) Oxygen Phosphorus Phosphorus Pentoxide Sulphur Sulphur Dioxide Sulphur Trioxide 33 .CHEMICAL SYMBOLS The following chemical symbols may be used where appropriate in the text.
325kPa a temperature TH of 298. ISO 6976-1983 (E).l-1 MJ µm Nm3 ppb ppm ppmv t t.y-1 °C K Unit of pressure (equivalent to one atmosphere) Giga Joule Kilogramme Kilogrammes per hour Kilowatt hour (1.h-1 kWh l m LHV m3 mg mg.15K (25°C) The deﬁnition of net caloriﬁc value is covered by an international standard. 34 .6GJ) Litre (liquid volume) Metre Lower Heating Value * Cubic Metre (liquid or solid volume) Milligramme Milligrammes per litre Mega Joule Micrometre Normal cubic metre (gas volume) Parts per billion Parts per million Parts per million by volume Tonnes (Metric Tons) Tonnes per day Tonnes per year Degree Celsius Degree Kelvin *Net caloric value or LHV Hi: The amount of heat evolved by the complete combustion of a unit volume of gas V (Tv: Pv) with air at a constant pressure of 101.d-1 t.000kWh = 3.UNITS Units have been standardised as far as possible and these are abbreviated as follows:bar GJ kg kg. The internationally applicable starting conditions are:an absolute pressure of 101.325kPa and a constant temperature TH when the combustion products have once more cooled to the starting conditions and whereby the water produced by the combustion is assumed to remain as vapour.
An extractive gas sampling system for continuous gas monitoring will typically comprise:– A coarse ﬁlter (heated if necessary) which may be in the stack or duct or outside – A heated line to convey the sample gas from the stack but this may not be necessary if probe dilution is used – A cooler may be used to reduce moisture – A further drier installed before the analyser – A pump. Methods available for monitoring the emissions given in Chapter 8 of this Booklet are brieﬂy described overleaf. Typical methods for monitoring emissions into water rely on ﬂow-proportioned sample collection or high frequency spot sampling together with analysis and continuous flow measurement. Introduction Monitoring of emissions plays an important part in environmental management. In general. manual methods may be more appropriate. as appropriate. the stability of the process and the reliability of the analytical method. 35 . Emission monitoring by regular spot checking in other cases will sufﬁce to survey the status and performance of equipment and to record the emission level. Iso-Kinetic sampling will be necessary when particulates are present. The use of trained staff is essential. the frequency of monitoring depends on the type of process and the process equipment installed. situated before or after the analyser. Vent streams are not normally measured by on-line methods and when measurements are required as base line checks. This can lead to rapid detection and recognition of irregular conditions and can give the operating staff the possibility to correct and restore the optimum standard operating conditions as quickly as possible.APPENDIX 1 EMISSION MONITORING IN AMMONIA PLANTS 1. It can be beneﬁcial in some instances to perform continuous monitoring. to pull the gas from the stack or duct – A ﬁne ﬁlter may be put immediately before the analyser National standards for gas sampling exist and the appropriate method should be adopted. The frequency will need to be balanced with a reasonable cost of monitoring. Manual methods may be necessary or accepted by the authorities in certain cases and for situations where no continuous method is available.
36 . 2.3. by capacitance or resistance measurements. the equipment consists of an optical ﬁlter. When the wavelength of the radiation is not selected using a prism or diffraction grating.2. In such cases a monthly check may be acceptable – refer to the manual methods section. The two beams are brought together onto a half-silvered mirror or rotating chopper which alternately allows each beam to reach a detector cell which compares the heat received. Flue-gas CO2.2 Sulphur Removal/Recovery SO2 and H2S Commonly used methods:SO2 – Infra Red Spectrometry (NDIR) Extractive sampling with appropriate sample conditioning is required. SO2. However. Emissions into Air 2. CO on-line analysis Commonly used methods:CO2 – Infra Red Spectrometry (Non-Dispersive Infra Red (NDIR)) NOx – Chemiluminescence SO2 – Infra Red Spectrometry (NDIR) CO – Infra Red Spectrometry (NDIR) or Electrochemical Extractive sampling with appropriate sample conditioning is used.1 Infra red spectrometry In the simplest form of IR spectrometry. The SO2 may also be calculated on the basis of measuring the input of sulphur to the system.3 On-Line Methods 2. the sample cell and a detector. regular zeroing and calibration are needed to correct zero and range drift. In a twin-beam instrument. the instrument is known as a non-dispersive infra red gas analyser (NDIR). (the most commonly used for on-line analysis) the radiation from the source is split and a comparison is made of the two beams after one has passed through a reference cell and the other through the sample gas. In a single-beam instrument a ﬁlter selects the part of the spectral range most characteristic of the substance. NOx. The twin-beam method is preferred in an on-line system as it overcomes some of the problems associated with drift due to small changes in detector sensitivity and in the optical and spectral properties of the optical ﬁlter. H2S – Routine manual sampling and analysis using instrumental methods such as electrochemical cells or gas chromatography with ﬂame photometric detection are required for accurate measurements 2.1. NOTE: It may be possible to determine CO2 by fuel speciﬁcation and energy consumption ﬁgures and the CO may be sufﬁciently low and stable to avoid the need for continuous monitoring.
37 . The extractive system should be designed to allow the elimination of H2O. The chemiluminescence (kv) is measured by a photomultiplier tube after passing through an appropriate band pass ﬁlter. NH3.3 Range of methods available Method Sulphur Dioxide Extractive NDIR Potential Interferences H2O. SO3 H2O.2. the chemiluminescence can be measured to determine the concentration of reacting gases. NO2 SO3 and particulates. As for extractive NDIR Comments The extraction system should be designed to allow the elimination of H2O. particulates and etching of the lens give problems. High moisture. By selecting two gases to react under carefully controlled conditions.2 Chemiluminescence These instruments use the property of ﬂuorescence which can take place with some chemical reactions. CO. SO3 and particulates. CO.3. NOx measurement makes use of the reaction:NO + O3 NO2 + O2 + kv The sample gas is passed through a catalytic converter to change any nitrogen dioxide to nitric oxide and is then reduced in pressure and reacted with ozone. Eliminate the effects of other UV absorbing compounds. Calibration may be difﬁcult. 2. NO2. H2S In-situ UV-visible Extractive ﬂuorescence Extractive ﬂame photometry Extractive electrochemical Sample requires conditioning to remove particulates and moisture to stop condensation and dissociation of salts. SO3. In-situ NDIR Extractive UV second derivative measurement Extractive NDUV CO2. NO. CO2. SO3 and particulates.3. hydrocarbons and particulates H2O NO2 H2O.
2.1 Sulphur dioxide Standard methods rely on the solubility and acidic nature of the gas.Method Oxides of Nitrogen Chemiluminescence In-situ NDIR Potential Interferences CO2. An alternative to this uses a sample collected in hydrogen peroxide solution and titration against barium perchlorate with thorin as indicator. 38 .3 are preferred. ﬁbre optic losses Straightforward conditioning Reduced accuracy due to interferences. Carbon Monoxide/Carbon Dioxide Extractive NDIR In-situ IR (ﬁbre optics) H2O and particulates Other IR absorbing components. An oxidising agent is generally used to convert the SO2 to SO3.2 Oxides of nitrogen The instrumental methods given in 2. A method which draws the ﬁltered gas through a standard solution of iodine in potassium iodide is also used. 2.4. The unreacted iodine is determined by titration with sodium thiosulphate and the SO2 calculated from the amount of iodine used to oxidise the SO2. H2O and NH3 H2O and particulates Comments Interferences can be reduced by precise selection of the wavelength.4. 2.4.3 Carbon monoxide/carbon dioxide These gases are generally measured by solution absorption into liquid reagents speciﬁc for each gas. All the methods have errors associated with the interferences and the user should be knowledgeable about the method and its suitability.4 Manual Methods 2. National standard methods include the use of hydrogen peroxide solution as the oxidising agent with titration against standard alkali or gravimetric analysis using barium chloride and hydrochloric acid to precipitate the sulphate. H2O. particulates.
37. Any suitable pH determination may be used and the free ammonia estimated as given in “Hampson B L. 3. The above method determines the NH4+ ammonia. Ass UK. it is probable that any site operating an ammonia plant will have at least one overall consent for emissions into water and a requirement for plant monitoring. Emissions into Water Whilst emissions into water are likely to be intermittent and of a low level. to form diacetyldihydrotoluidine.3. Typical monitoring methods may rely on ﬂow proportioned sample collection or high frequency spot sampling and ﬂow measurement. it may be more important to relate the NH4+ result to free ammonia. In either case the samples obtained may be analysed as follows:- 3. Free ammonia is particularly toxic to ﬁsh and should an incident occur. estuarine or sea water) and may be used in continuous ﬂow colorimetry. 1974. Note that free ammonia exists in equilibrium with NH4+ as follows:NH4+ + H2O NH3 + H3O+ and that the equilibrium depends on pH. Manual laboratory based methods may be used for spot checks using Kjeldahl methods for the determination of organic and ammoniacal nitrogen in a mineralised sample. J Mar Biol.54. 39 . Mer. The formaldehyde is reacted with acetylacetone in the presence of excess ammonium salt. 562”.2 Methanol The spectrophotometric method for methanol relies on the oxidation reactions of potassium permanganate under acid conditions to give formaldehyde. The method may be used in continuous ﬂow colorimetry or gas chromatography. Ion selective electrodes can also be used and are suitable for saline applications as well as pure water.1 Ammonia/Ammoniacal N The spectrophotometric method for ammonia relies on the reaction in which monochloramine is reacted with phenol to form an indophenol blue compound. 11” and “Whitﬁeld M. 1977. J Cons Int Explor. This method is particularly suitable for the determination of ammonia in cooling waters derived from saline sources (dock.
cm-3 (at 0°C.4°C at 101. 3.7 : –77. 101.7714g.l-1 at 20°C : Soluble in alcohol. Hazards to Man and the Environment To man Ammonia is toxic by inhalation and pulmonary oedema may occur up to 48 hours after severe exposure and could be fatal. Vapours cause irritation and watering of eyes and in the presence of moisture.S.6386g. Physical and Chemical Properties Appearance Odour pH water solution (1%) Melting point (triple point) Boiling point Explosive limits Auto-ignition temperature Vapour pressure Relative vapour density Solubility in water Solubility in organic solvents Liquid density Gas density 40 : Colourless liqueﬁed gas : Pungent. To the environment Ammonia is toxic to aquatic life. Liquid ammonia splashes may produce severe burns to the skin and permanent damage to the eyes.3kPa : 16-27% NH3 by vol.3kPa) : 0.APPENDIX 2 GENERAL PRODUCT INFORMATION ON AMMONIA 1. suffocating : 11. in air at 0°C : 651°C : 1013kPa at 25°C : 0. 101.6 (air =1) : 529g. Registry number EINECS Number EINECS Name Molecular formula : Ammonia : Liquid Ammonia : 7664-41-7 : 231-635-3 : Anhydrous Ammonia : NH3 2. acetone. closed workshops) ammonia vapour may be ﬂammable/explosive.3kPa) . irritation of the skin.l-1 (at 0°C.A. In enclosed spaces (eg vessels. Identiﬁcation Name Commonly used synonyms C.7°C : –33. chloroform : 0.
Production of NPK Compound Fertilizers by Mixed Acid Route Printed by Fisherprint Ltd. England . Production of Nitric Acid 3. Production of NPK Compound Fertilizers by Nitrophosphate Route 8. Production of Sulphuric Acid (in collaboration with ESA) 4. Production of Ammonia 2.Best Available Techniques Booklets were ﬁrst issued by EFMA in 1995 Second revised edition 2000 1. Production of Ammonium Nitrate and Calcium Ammonium Nitrate 7. Production of Phosphoric Acid 5. Production of Urea and Urea-Ammonium Nitrate 6. Peterborough.